Disazo dyes containing an alkoxy-halogen-triazine group

ABSTRACT

A DISAZO COMPOUND OF THE FORMULA   2-(Y-R1-N=N-),3-(H-O3S-),5,6-BIS(Y-),7-(X-R2-N=N-),   8-(H2N-)-NAPHTH-1-OL   IN WHICH ONE OF THE SYMBOLS Y REPRESENTS A HYDROGEN ATOM AND THE OTHER SYMBOL Y REPRESENTS A SULPHONIC ACID GROUP, R1 AND R2 EACH REPRESENTS AN AROMATIC RESIDUE CONTAINING A SULPHONIC ACID GROUP, ONE OF THE SYMBOLS X REPRESENTS A FIBRE-REACTIVE ALKOXY-HALOGENO-TRIAZINE GROUP BOUND TO THE AROMATIC RESIDUE BY WAY OF AN-NH GROUP, THE ALKOXY RESIDUE CONTAINS AN ETHERIFIED ALKYL RESIDUE, AND THE OTHER SYMBOL X REPRESENTS A HYDROGEN ATOM OR A FIBREREACTIVE ACYL RESIDUE BOUND TO THE AROMATIC RESIDUE BY WAY OF AN-NH GROUP.

United States Patent ifice 3,663,526 DISAZO DYES CONTG AN ALKOXY- HALOGEN-TRIAZINE GROUP Fritz Oesterlein, Basel, and Karl Seitz, Oberwil, Basel- Land, Switzerland, assignors to Cilba-Geigy AG, Basel, Switzerland No Drawing. Filed Oct. 15, 1969, Ser. No. 866,724 Claims priority, application Switzerland, Nov. 4, 1969, 16,383/69 Int. C1. C09]: 62/08 US. Cl. 260-153 6 Claims ABSTRACT OF THE DISCLOSURE A disazo compound of the formula HO N H:

in which one of the symbols Y represents a hydrogen atom and the other symbol Y represents a sulphonic acid group, R and R each represents an aromatic residue containing a sulphonic acid group, one of the symbols X represents a fibre-reactive alkoxy-halogeno-triazine group bound to the aromatic residue by way of an NH group, the alkoxy residue containing an etherified alkyl residue, and the other symbol X represents a hydrogen atom or a fibrereactive acyl residue bound to the aromatic residue by way of an NH group.

This invention provides disazo compound of the formula H(|) NH:

HOsS- -Y in which one of the symbols Y represents a hydrogen atom and the other symbol Y represents a sulphonic acid group, R and R each represents an aromatic (component) residue containing a sulphonic acid group, and one of the symbols X represents .a fibre-reactive alkoxy-halogeno-triazine group bound to the aromatic residue by way of an NH group, the alkoxy residue containing an etherified alkyl residue, and the other symbol X represents a hydrogen atom or a fibre-reactive acyl residue bound to the aromatic residue by way of an NH group.

The compounds of Formula 1 may be obtained (a) by coupling compounds of the formula (2) HO I\|TH1 in which Y has the meaning given above, on one side with a diazo compound of an amine of the formula X--R -NH in which R has the meaning given above and X represents a hydrogen atom or a fibre-reactive acyl residue bound to R by way of an NH group, especially an alkoxy-halo- 3,663,526 Patented May 16, 1972 gen-triazine group bound through an NH group, and on the other side with a diazo compound of an amine of the formula H NR X, in which R has the meaning given above and X represents a hydrogen atom or a fibrereactive acyl residue bound to R by way of an --NH group, especially an alkoxy halogeno triazine group bound through an NH group, X representing an alkoxyhalogeno-triazine group when the first-mentioned diazo component does not contain such a group, to form a compound of Formula 1 or (b) by condensing compounds of the formula HO lTTHg in which Y has the meaning given above and R1 and R;

each represents an aromatic residue, one of which contains an acylatable amino group and the other can contain an acylatable amino group, with alkoxy-dihalogenotriazines and, if necessary, with further acylating agents containing fibre-reactive residues, to form compounds of Formula 1.

The amines of the formulae XR NH and in which R R and X have the meanings given above, or the compounds of the Formula 3, in which 1, 5 and Y have the meanings given above, used as starting materials for process (b) of the invention can contain further substituents in the aromatic residues R R R; and R;

in which R R and X have the meanings given above, the amines hereinafter mentioned and also the condensation products thereof with the acylating agents listed below which contain fibre-reactive residues may be used, especially condensation products with alkoxy-halogeno-triazines, it being essential that the acylated amines also contain a further diazotizable amino group to enable coupling with the 1amino-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid used as starting material in accordance with process (a), or with the corresponding monoazo compound obtained from 1amino8-hydroxynaphthalene-3,6- or 4,6-disulphonic acid by unilateral coupling with a diazo compound derived from an amine of the formula The following are given as examples:

1-aminobenzene-2-, -3- or -4-sulphonic acid, 1-aminobenzene-2,S-disulphonic acid, 1-amino-4-methylbenzene-Z-sulphonic acid, 1-amino-5-acetylaminobenzene-2-sulphonic acid, l-amino-4-acetylaminobenzene-2-sulphonic acid, 1-amino-4-nitrobenzene-2-sulphonic acid, 1-amino-6-methylbenzene-2,4-disulphonic acid, 1-amino-4-methoxybenzene-Z-sulphonic acid, 1-amino-4,6-dimethylbenzene-2-sulphonic acid, 1-amino-S-fluorobenzene-Z-sulphonic acid, 1-aminobenzene-2,4,6-trisulphonic acid, 1-amino-4,a-sulphoacetylaminobenzene-2-sulphonic acid, 1-amino-5,a-sulphoacetylaminobenzene-Z-sulphonic acid, l-aminobenzene-2,4-disulphonic acid, -1-amino-4-chlorobenzene-Z-sulphonic acid, 1-amino-2-methoXybenzene-4- or -5-sulphonic acid, 1,3-diaminobenzene-G-sulphonic acid, 1-amino-2'-carboxybenzene-4-sulphonic acid, 2-aminonaphthalene-4,6,8-trisulphonic acid, Z-amino-6-nitronaphthalene-4,8-disulphonic acid, 1-amino-3-carboxybenzene-6-sulphonic acid, 4-aminodiphenyl-3-sulphonic acid, l-amino-2-chlorobenzene-4-sulphonic acid, 1-amino-2-ethylbenzene-4-sulphonic acid, l,4-diaminobenzene-Z-sulphonic acid, 1,4-diamino-3-methylbenzene-6-sulphonic acid, 1-amino-2-methyl-5-chlorobenzene-4-sulphonic acid, 1,4-diaminobenzene-2,5-disulphonic acid, 1,4-diaminobeuzene-2,6-disulphonic acid, 1,3-diaminobenzene-4,6-disulphonic acid, 1,3-diamino-2,4,G-trimethylbenzene-S-sulphonic acid, l-amino-3-nitrobenzene-S-sulphonic acid, 1-amino-3-acetylaminobenzene-S-sulphonic acid, 1-amino-4-phenylaminobenzene-3-sulphonic acid, 1-amino-4-(4'-aminophenylamino)-benzene-3-sulphonic acid, 4-aminodiphenyl-3,3-disulphonic acid, 4,4'-diaminodiphenyl-3,3'- or -2,2'-disulphonic acid, 1,4'-diamino-4-phenylamino-2,2-disulphonic acid, 4,4'-diaminostilbene-3,3'-disulphonic acid, 1-aminonaphthalene-3- or -4-sulphonic acid, 2-aminonaphthalene-5-, -6-, -7- or -8-sulphonic acid, -1-aminonaphthalene-5-, -6-, -7- or -8-sulphonic acid, Z-aminonaphthalene-lor -8-sulphonic acid, 1-aminonaphthalene-3,6- or 4,6-disulphonic acid, 1-arninonaphthalene3,8-disulphonic acid, 2-aminonaphthalene-4,8- or -6,8-disulphonic acid, 1-aminonaphthalene-3,6,8-trisulphonic acid, 2-aminonaphthalene-3,6,8-trisulphonic acid, 1-aminonaphthalene-4,6,8-trisulphonic acid, 2-aminobenzthiazole-5- or -6-sulphonic acid, 1-aminopyrene-3- or -4-sulphonic acid, and 3-aminopyrene-diand tri-sulphonic acid.

Disazo compounds of Formula 1 which are of special interest are those in which X and Y have the meanings ascribed to them in the said formula and in which R and R each represents a monosulphoor disulphobenzene residue.

The disazo compounds of Formula 1, in which the residues R and R are benzene residues, that are worthy of special mention are those which contain a sulphonic acid group in ortho-position to the azo group and in which the acylamino group, which contains a fibrereactive residue, is situated in meta-position to the azo group. These disazo compounds preferably contain only one fibre-reactive group.

Diazotization of the amines used in accordance with the invention, for example, those indicated above, and the coupling thereof with the 1-amino-S-hydroxynaphthalene- 3,6- or -4,6-disulphonic acid used as starting material can be carried out successively, it being advantageous first to effect acidic coupling and then alkaline coupling. In an acidic solution coupling takes place at a position vicinal to the amino group of the starting component, and in a slightly acid to weakly alkaline solution the second diazo component couples at a position vicinal to the hydroxyl group of the starting component. One of the amines used as diazo component can be free from acyl groups containing fibre-reactive residues, but both amines may contain such an acyl group, in which case it is preferable that the acyl groups be identical. In any case, one of the two amines must contain an alkoxy-halogeno-triazine group as fibre-reactive acyl residue. When the end product is to contain only one reactive group, this is advantageously introduced with the diazo component which couples in an alkaline medium.

Diazotization of the amines used in accordance with the present invention may be etfected by known methods, for example, with hydrochloric acid and sodium nitrite. Coupling may also be carried out according to known methods in an acid medium and in a slightly acid to weakly alkaline medium.

Preparation of the amines of the formulae in which R and R have the meanings given above and X represents an acyl residue containing a fibre-reactive residue and which is bound to R or R by way of an -NH group, the fibre-reactive residue being for example one of the aliphatic or heterocyclic fibre-reactive residues mentioned below or especially an alkoxy-halogenotriazine residue in which the alkoxy residue contains an etherified alkyl residue, may be effected by condensing diamines of the formula with the corresponding acylating agents which react with an amino group with formation of a fibre-reactive grouping.

By fibre-reactive substituent is meant a reactive grouping capable of reacting with the hydroxyl groups of cellulose or with the carboxylic acid amide groups of polyamides with formation of a covalent bond. Residues of the kind defined are aliphatic and especially heterocyclic residues; fibre-reactive diazine and especially triazine substituents are preferred.

The following are examples of suitable acylating agents having a reactive acyl residue: the anhydrides or acid halides of aliphatic a,fl-unsaturated carboxylic acids, for example, chloromaleic anhydride, propiolic acid chloride, acrylic acid chloride and especially the halides of aliphatic carboxylic acids containing exchangeable halogen atoms, for example, chloroacetyl chloride, sulphochloro-acetic acid chloride, fl-bromoor chloro-propionic acid chloride, 0:,fi-di6h1010- or -dibromo-propionic acid chloride, fluorocyclobutane-carboxylic acid halides, for example, triand tetra-fiuorocyclobutane-canboxylic acid chlorides, a-ChlO- roor u-bromo-acrylic acid chloride or bromide, and also heterocyclic acylating agents, for example, 2-halogenobenzthiazoleor -oxazolecarboxylicor -sulphonic acid chloride, 3,6-dichloropyridazine-5-carboxylic acid chloride, tetrachloropyridazine, 4,5 dichloropyridazon-(6)- yl-propionic acid chloride, 4,5 dichloro l phenylpyridazone-carboxylic or -sulphonic acid chloride, 4,5-dichloropyridazone-propionic acid chloride, 1,4-dichlorophthalazine-carboxylic or -sulphonic acid chloride, 2,3-dichl0roquinoxaline-carboxylic or -sulphonic acid chloride, 2,4-dichloroquinazoline-carboxylic or -sulphonic acid chloride, 2,4,6-trichloroor 2,4,6-tribromopyrimidine and the derivatives thereof which contain, for example, in S-position a cyano, nitro, methyl, ethyl, carboxylic acid amide, sulphamide, carbomethoxy, carbalkoxy, acyl (for example, benzoyl, acetyl or propionyl), alkenyl (for example, allyl or chlorovinyl) group or a substituted alkyl group (for example, carboxymethyl, chloromethyl or bromomethyl group), 2,4,5,6-tetrachloroor 2,4,5,6-tetra-bromopyrimidine, 2,6 dichloroor 2,6-dibromo-4-carboethoxypyrimidine, 2,4,5 trichloropyrimidine, 5 nitro-6-methy-2,4-dichloropyrirnidine, 2,4 dichloropyrimidine 6-carboxylic acid chloride, 2,4 dichloropyrimidine-S-carboxylic acid chloride, 2,6 dichloroor 2,6-dibromopyrimidine-4- or -5 carboxylic acid or sulphonic acid amides or -4- or -5- carboxylic acid or -sulphonic acid chloride, 2,4 dichloropyrimidine-S-sulphonic acid, 2,4-dichloro-S-chloromethyl- 6-methylpyrimidine, 2,4-dibromo-S-bromomethyl-G-methylpyrimidine, 2,4-dichloro-5-chloromethylpyrimidine, 2,4- dibromo 5 bromomethylpyrimidine, 2,5,6 tric1oro-4- methylpyrimidine, 2,6 dichloro-4trichloromethylpyrimidine or especially 2 methanesulphonyl-4,5-dichloro-6- methylpyrimidine, 2,4 dimethanesulphonyl 5-chloro-6- methylpyrimidine, 2,4,6 trichloro-l,3,5-triazine or 2,4,6- tribromo 1,3,5-triazine and 4,6-dichloro-1,3,5-triazines that are substituted in 2 position by an aryl or alkyl residue, for example, a phenyl, methyl or ethyl residue, or by the residue of an aliphatic or aromatic mercapto or hydroxyl compound bound by Way of the sulphur or oxygen atom respectively, or especially by an amino group or by the residue of an aliphatic, heteroaliphatic or aromatic amino compound bound through its nitrogen atom. The following are examples of compounds of the kind mentioned the residues of which can 'be bound to the triazine nucleus at 2 position by reaction with trihalogeno-triazines: aliphatic or aromatic mercapto or hydroxyl compounds, for example, thioalcohols, thioglycollic acid, thiourea, thiophenols, methyl alcohol, ethyl alcohol, isopropyl alcohol, glycollic acid, phenol, chloroor nitro-phenols, phenol carboxylic and phenol sulphonic acids, naphthols, naphthol sulphonic acids, and so forth, but especially ammonia and compounds containing acylatable amino groups, for example, hydroxylamine, hydrazine, phenylhydrazine, phenylhydrazine sulphonic acid, carbamic acid and the derivatives thereof, semiand thiosemi-carbazides and -carbazones, methylarnine, ethylamine, isopropylamine, methoxyethylamine, methoxypropylamine, dimethylamine, diethylamine, methylphenylamine, ethylphenylamine, chloroethylamine, ethanolamines, propanolamines, benzylamine, cyclohexylamine, morpholine, piperidine, piperazine, aminocarbonic acid esters, aminoacetic acid ethyl esters, aminoethane sulphonic acid, N-methylaminoethane sulphonic acid, and especially aromatic amines, for example, aniline, N-methylaniline, toluidines, xylidines, chloroanilines, paraor meta-aminoacetanilide, nitroanilines, aminophenols, nitrotoluidines, phenylenediamines, toluylenediamines, anisidine, phenetidine, diphenylamine, naphthylamines, aminonaphthols, diaminonaphthalenes, and especially anilines containing acidic groups, for example, sulphanilic, metanilic and orthanilic acid, aniline disulphonic acids, aminobenzyl sulphonic acids, aniline, wmethane sulphonic acid, aminodibenzoic acids, naphthylamine-diand -tri-sulphonic acids, aminobenzoic acids, for example, 1- or 2 hydroxy-S-aminobenzoic acid, aminonaphthol-mono-, -diand -tri-sulphonic acids, aminobenzoic acid-sulphonic acid, and so forth, and also coloured compounds having dyestufi' characteristics, for example, 4-nitro-4'-aminostilbene disulphonic acid and aminoazo dyestufis or arninoanthraquinones or phthalocyanines that also contain at least one reactive amino group. i

The acylation process (condensation) can be performed in known manner, for example, in an aqueous medium in the presence of an agent capable of binding acid, for example, sodium hydroxide or sodium carbonate.

The introduction of the triazine residues substituted in 2-position by the residue of a hydroxyl, mercapto or amino compound or ammonia and especially by the alkoxy residues mentioned below containing an etherified alkyl residue into the compounds of Formula 2 can also be effected by first acylating the starting diamine with a 2,4, 6-trihalogeno-1,3,5-triazine, especially cyanuric chloride, and then replacing a halogen atom in the dihalogeno-triazine compound so obtained by reaction with one or a plurality of the above mentioned compounds before or after coupling the diazotized acylated diamine with the 1- amino-8-hydroxynaphthalene-3,6- or -4,6'disulphonic acid to form a compound of Formula 1.

Of the acylating agents containing an alkoxy-halogenotriazine residue in which the alkoxy group containing up to 7 carbon atoms and carries an etherified alkyl group containing up to 6 carbon atoms, including cyclic ether groupings, for example, the oxacyclopentyl residue, those of special value contain an alkylene bridging component that may be branched and that contain at least 2, but preferably not more than 4 carbon atoms. The following are given as examples: 13-methoxy-ethoxy-, 'y-methoxypropoxy-, methoxy-isopropoxy-, methoxy-butoxy-, 6- methoxy-butoxy-, B ethoxy-ethoxy-, ethoxy-isopropoxy-, ethoxy-butoxy-, ethoxy-isobutoxy-, fi-propoxy-ethoxy-, 'ypropoxy-propoxy-, y-isopropoxy-propoxy-, [3 n butoxyethoxy-, isopropoxy-butoxy-, n-hexoxy-ethoxy-, oxacyclopentylmethoxy-, B-(B-methoxyethoxy) ethoxy-, S-(B-ethoxy-ethoxy)-ethoxy-, fi-(B-isopropoxyethoxy)-ethoxy-, ,8- ethoxy-ethoxy-methoxy-, fl-ethyl-mercapt0-ethoxy-, 19-phenoxy-ethoxy-, para-methoxy-benzyloxy-, diethoxy-isopropoxy-, ,8-allyloxy-ethoxy-, fl-vinyloxy-ethoxy-, B-proparglyoxy-ethoxy-, 'y-ethoxy-propoxy-dichloroor -dibromo-l,3, S-triazine.

These alkoxy-halogeno-triazines can be prepared by reacting a 2,4,6-trichloroor -tribromo-l,3,5-triazine with an alcohol in the presence of an agent capable of binding acid, preferably in the absence of water.

The alcohols that can be used for the condensation are the alkoxy-alkanols corresponding to the alkoxy-alkoxy groups, for example, ethoxyethanol, isopropoxypropanol, hexoxyethanol, methoxybutanol, and so forth.

The starting materials required for process (b) of the invention can be obtained by coupling 1-amino-8-hydroxynaphthalene-3,6- or -4,6-disulphonic acid in known manner with diazotized monoamines or diarnines, or monoamines containing a group convertible into a free H N- group, for example, a nitro group, for example with those mentioned in the description of process (a) which are free from acyl residues containing fibre-reactive groups. In this case too, it is advantageous first to couple in an acidic medium and then in an alkaline medium as in process (a). Subsequently, acylation to form the disazo compounds of Formula 1 is effected, one of the acyl groups introduced being essentially an alkoxy-halogeno-triazine group in which the alkoxy reidue contains an etherified alkyl residuepSuitable acylating agents are those recommended for process (a).

Condensation of these acylating agents with the compounds of Formula 3 in accordance with the invention may be carried out by known methods, advantageously in the presence of an agent capable of binding acid, for example, sodium acetate, sodium hydroxide or sodium carbonate, and under conditions such that at least one exchangeable substituent, for example, a halogen atom, remains in the end product, that is to say, for example, in the presence of an organic solvent or at a relative low to moderately elevated temperature in an aqueous medium. When a cyanuric halide is used, especially cyanuric chloride, the dihalogeno-triazine compound that is first formed can be converted into a monohalogeno-triazine compound by subsequent exchange of a further halogen atom for one of the residues indicated, as already mentioned in respect of the dihalogeno-triazines prepared by coupling. The reactants used in this method of preparation are the above mentioned mercapto, hydroxyl and amino compounds, and the reaction conditions are preferably also the same as those described above.

The compounds obtained by coupling or acylation in accordance with the processes of the invention are new.

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.lzmm MHz 835 @335 :3 5 m5 w 3. mmomn H HHH E H 21 EXAMPLE 2 23 parts of 3-acetylamino-1-aminobenzene-6-sulphonic acid are diazotized and coupled with a solution of 31.9 parts of 1 amino-8-hydroxynaphthalene-3,6-disulphonic acid at 15 C. When coupling is finished the batch is neutralized to pH 5 with a sodium hydroxide solution. A further 23 parts of 3-acetylamino-l-aminobenzene-6-sulphonic acid are diazotized and coupled at pH 6 to form the disazo dyestuif. Sodium hydroxide solution is then added to the dyestuff solution so that a 4% solution is formed, and the acetyl group is hydrolysed by heating for 4 hours at 90 C. The batch is then neutralized to pH 7 with hydrochloric acid, cooled to 30 C. and condensation is carried out at 30 C. with 44.8 parts of methoxyethoxydichlorotriazine. The hydrochloric acid that is liberated is neutralized by the dropwise addition of 100 parts of a 2 N sodium hydroxide solution. The dyestufi is precipitated by the addition of sodium chloride, isolated by filtration and dried. The dyestuif so obtained dyes cotton a greenish blue shade.

Dyeing procedure 2 parts of dyestufi are dissolved in 100 parts of water. A cotton fabric is impregnated with the solution so obtained in a manner such that its weight is increased by 75% and then dried.

The fabric is then impregnated at 20 C. with a solution containing 10 grams of sodium hydroxide and 300 grams of sodium chloride per litre, squeezed to a weight increase of 75 steamed for 60 seconds at 100 to 101 C., rinsed, soaped for minutes in a 0.3% solution of a non-ionic detergent at the boil, rinsed and dried.

Printing procedure 30 parts of dyestutf and 150 parts of urea are dissolved in 380 parts of water, and the solution so obtained is stirred into 400 parts of a 5% aqueous sodium alginate thickener. 30 parts of sodium bicarbonate and 10 parts of an oxidizing agent (for example, Albatex BD=sodium meta-nitrobenzene sulphonate) are then added while stirring.

A cotton fabric is printed with this printing paste and dried. The fabric thus treated is then steamed for 1 to 2 minutes at 100 to 102 C., rinsed thoroughly in cold water, then in hot water and dried.

We claim: 1. A disazo compound of the formula R1N=N -N=-NRz Ho s Y in which one of the symbols Y represents hydrogen and the other symbol Y represents sulphonic acid, R and R are each sulfophenyl or sulfophenyl substituted by chloro, bromo, fluoro, u-sulfoacetylamino, methyl, ethyl, methoxy, ethoxy, acetylamiuo, propionylamino, benzoylamino, phenyl, p-chlorophenyl, nitro, sulfo, carboxyl or a triazine group of the formula wherein OR is alkoxy of up to 7 carbon atoms and OR is alkoxy of up to 6 carbon atoms; in which at least one of R and R contains said triazine group.

2. The compound of claim 1 wherein R and R are each sulfophenyl or sulfophenyl substituted by sulfo.

3. A disazo compound of the formula SO H HO NH: SOaH I Cl-C in which n=1 or 2.

4. A dyestutf that in its free acid state corresponds to the formula l Cl-C J-OCHaCHzO CHaCH;

5. A dyestuff that in its free acid state corresponds to the formula SiO 6H H O IIIH: S 0 3H 1 I311 H0 3 S03H 30 E 01-5 (J-O CHaCHzOCHg 6. A dyestuff that in its free acid state corresponds to the formula JOSEPH REBOLD, Primary Examiner D. M. PAPUGA, Assistant Examiner US. Cl. X.R.

260154, 248 CS, 249.5, 249.8, 251 R, 256.4 R; 8-21, 41 R, 163

QE'NFEQATE @IF @QREQTEQN Patent No. 3,663,526 I Dated M y 16, 1972 Inventor(s) Fritz Oesterlein vet a1,

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 22, in the center portion of the formula of claim 3,

" 7 HO NH shouldbe (SEAL) Attest:

EDWARD M.FLET CHER,JR. RENE D. TEGTMEYER Attesting Officer Acting Commissioner of Patents 

